Process for reducing filler loss

ABSTRACT

The agglomeration of finely divided granular tetrafluoroethylene polymer particles to produce agglomerated particles having improved flow properties is carried out by agitating the finely divided particles in an aqueous dispersion containing a substantially water-immiscible organic liquid. The finely divided particles can first be blended with particulate hydrophilic filler material and the blend agglomerated. The presence of both an amino-functional organosilane and a silicone resin while agitating the aqueous dispersion of the blend of the filler material and the finely divided tetrafluoroethylene polymer effectively reduces loss of filler during the agglomeration procedure.

United States Patent 1 Leverett PROCESS FOR REDUCING FILLER LOSS Glenn Frederick Leverett, Vienna, W. Va.

[73] Assignee: -E. I. Du Pont de Nemours and Company, Wilmington, Del.

[22] Filed: Dec. 11, 1974 [21] Appl. No.: 531,481

Related 0.8. Application Data [63] Continuation-impart of Ser. No. 473,158, May 24,

1974, abandoned.

[75] Inventor:

[52] US. CL... 260/29.6 F; 260/33.6 F; 260/33.8 F; 260/34.2; 260/42.26; 260/42.27;

[51] Int. Cl. C08K 5/01; C08K 5/02; C08L 27/18; C08L 43/04 [58] Field of Search 260/29.6 F, 33.6 F, 33.8 F, 260/34.2, 42.26, 42.27, 42.49, 827

[ Oct. 28, 1975 Primary Examiner-Donald E. Czaja Assistant Examiner-H. H. Fletcher [5 7] ABSTRACT The agglomeration of finely divided granular tetrafluoroethylene polymer particles to produce agglomerated particles having improved flow properties is carried out by agitating the finely divided particles in an aqueous dispersion containing a substantially waterimmiscible organic liquid. The finely divided particles can first be blended with particulate hydrophilic filler material and the blend agglomerated. The presence of both an amino-functional organosilane and a silicone resin while agitating the aqueous dispersion of the blend of the filler material and the finely divided tetrafluoroethylene polymer effectively reduces loss of filler during the agglomeration procedure.

9 Claims, N0 Drawings PROCESS FOR REDUCING FILLER LOSS CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of application Ser. No. 473,158 filed May 24, 1974, and now abandoned.

FIELD OF THE INVENTION This invention relates to the agglomeration of blends of granular tetrafluoroethylene polymer particles and particulate hydrophilic fillers.

BACKGROUND OF THE INVENTION The practice of agglomerating finely divided granular tetrafluoroethylene polymer particles to increase their flowability while retaining their moldability properties is known. One method of agglomerating the finely divided granular tetratluoroethylene polymer particles is to agitate them in a two phase liquid medium of water containing an organic liquid that is capable of wetting the particles and which is soluble in water to at most only about percent by weight at the operating temperature. The solubility requirement means that the organic liquid is substantially immiscible in water.

It is also known that blends of the finely divided polymer particles and particulate filler materials can be agitated and agglomerated in the same manner. However, if the filler material is hydrophilic, filler is lost to the aqueous phase during the agglomeration process.

Such loss is undesirable for several reasons. For example, quality standards are difficult to maintain since the loss can vary from batch to batch. Moreover, it is costly to recover lost filler from the aqueous phase and costly to be forced to use more filler than necessary in the initial blend in order to get approximately the right amount in the agglomerated product. In addition, the loss is visibly noticeable in the final molded product because of loss of filler from the surface of each agglomerated particle.

Certain organofunctional silane and silicone compounds are known to be useful in coupling resins with fillers to improve the strength of the molded resin. But with granular polytetrafluoroethylene resins the filler has heretofore been treated with the silane or silicone resin prior to mixing the tiller with the resin, and filler loss has not been prevented.

SUMMARY OF THE INVENTION The invention described herein is a process for preparing agglomerated granules of granular tetrafluor- DESCRIPTION OF THE INVENTION In general, the agglomeration of granular tetrafluoroethylene polymers is well known. The tetrafluoroethylene polymers used are unsintered, are of the granular type made by suspension polymerization (as distinguished from the fine powder type made from aqueous dispersion polymerization), and are non-meltfabricable.

By tetrafluoroethylene polymer is meant the homopolymer of tetrafluoroethylene (PTFE) and copolymers thereof wherein the amount of comonomer present is polymerized form is small enough to maintain the non-melt-fabricable nature of the copolymer. Generally, this small amount will be less than about 2 percent by weight of the copolymer. The comonomer can be an ethylenically unsaturated copolymerizable monomer, such as a perfluoroalkene of 3-6 carbon atoms, e.g., hexafluoropropylene, or a perfluoro(alkyl vinyl ether) of 3-6 carbon atoms, e.g., perfluoro(propyl vinyl ether). These polymers are not melt-fabricable, i.e., they have an apparent melt viscosity of at least 1 X 10 poises at 380C. The melt viscosity is measured according to American Society of Testing Materials Test D- 123 8-52T, modified as described following. The cylinder, orifice and piston tip are made of a corrosionresistant alloy, Haynes Stellite 19, made by Haynes Stellite Co. The sample is charged to the 9.53mm. inside diameter cylinder, which is maintained at 372C. i 1C. Five minutes after the sample is charged to the cylinder it is extruded through a 2.1mm. diameter, 8mm. long orifice under a load (piston plus weight) of 5000 grams. This corresponds to a shear stress of 0.45 kilograms per cm The melt viscosity in poises is calculated as 53,150 divided by the observable extrusion rate in grams per minute.

Tetrafluoroethylene polymer granules, as obtained from suspension polymerization, have an average diameter of about 1000 microns. For use in the agglomeration procedure, these granules are ground into finely divided particles of an average particle size based on the number of particles of below about 200 microns and usually to about an average size of less than about microns, for the ability to obtain agglomerates having good molding properties depends on the small initial particle size of the polymer to be agglomerated. The particle size will depend on the degree of grinding. Generally, the average size should be at least about 5 microns.

The substantially water-immiscible organic liquid used should have sufficient immiscibility with the water and sufficient wettability for the finely divided tetrafluoroethylene polymer to cause formation of the agglomerates on agitation. Generally, the immiscible organic liquid can be soluble in water up to 15 percent by weight at the operating temperatures of the process. Preferably the solubility will be less than 1 percent. The organic liquid should be present in the water in an amount sufficient to provide a non-aqueous phase. The wettability of the organic liquid can be expressed through its surface tension, which should be no greater than about 40 dynes/cm at 25C. Generally, the surface tension should be at least about 10 dynes/cm at 25C. Examples of organic liquids useful herein include aliphatic hydrocarbons, such as pentane and dodecane; alicyclic hydrocarbons, such as cyclohexane or methyl cyclohexane; aromatic hydrocarbons such as benzene, toluene or xylene; and halogenated hydrocarbons, such as, tetrachloroethylene, trichloroethylene, chloroform or chlorobenzene; and the like. Generally, the hydrocarbons will contain no more than 12 carbon atoms. The organic liquid generally is present in an amount between 0.1 to 0.5 cc of the organic liquid per gram of tetrafluoroethylene/filler blend employed. The exact amount employed will influence the particle size of the agglomerated filled tetrafluoroethylene polymer.

The water can be demineralized if desired, but such is not necessary.

The particulate fillers used herein include the usual hydrophilic mineral, metallic or glass filler such as glass fibers, glass beads, powdered bronze, asbestos, graphite, mica, alumina, and the like. These are commercially available fillers for filling resins. The filler may be present in an amount of from 5 to 40 percent by volume based on the volume of the tetrafluoroethylene and the filler. The filler, when in particle form. i.e., bead or powder, should preferably have an average size no greater than about the size of the resultant agglomerates and most preferably smaller so that in the resultant agglomerates, which are usually of 250 to 1000 micron average particle size, the filler particles are largely enveloped by the polymer. When in fiber form the length of the fiber preferably should be less than the size of the resulting agglomerate and when in flake form the largest length of the flake should preferably be less than the size of the resulting agglomerate. However, protruding portions of the fiber flake or particle are not substantially deleterious to powder flow.

The amino-functional organosilane has at least one water-hydrolyzable functional group attached directly to the Si atom of the silane and at least one aminofunctional containing organic group connected directly to the silicon atom of the silane through a stable carbon-to-silicon bond. It is believed that the waterhydrolyzable functional group of the silane forms a bonding relationship with the filler and the aminofunctional group forms a bonding relationship with the PTFE, thereby coupling the filler to the PTFE. These silanes can be described in greater detail as being represented by the formula wherein A is the water-hydrolyzable functional group, B is the organic group containing the amino-functional group, and each D can be either A, B, or an alkyl group, preferably containing from 1-5 carbon atoms, or aryl, preferably containing from 6-10 carbon atoms, or alkaryl, preferably containing 7-10 carbon atoms, or aralkyl, preferably containing 7-10 carbon atoms. Examples of group A include hydroxyl, halogen such as C1 or F; or alkoxy, preferably containing from 1 to 5 carbon atoms. Examples of group B include aliphatic and aromatic hydrocarbyl groups of 1-14 carbon atoms containing amino-functionality in which the aminofunction can be primary, secondary or tertiary. Thus,

B includes GNP bonded directly to the Si atom or indirectly thereto, such as though an alkylene group of 1-4 carbon atoms; (CH ),NH wherein x is an integer of from 2 to 12, but preferably 3 to 9; (CH- ),,NH(Cl-l- NHR wherein y is an integer of from 2 to 4, and z is an integer of from 1 to 4, and R is H, methyl or ethyl; and -(Cl-l ),N(CH wherein x has the same meaning before. Preferred silanes include the omegaaminoalkyltrialkoxy silanes, such as gammaaminopropyltriethoxy silane, meta and para aminophenyltriethoxy silane, and N(n-propyl trimethoxysilyl) ethylene diamine. The amino-functional organosilane can be present in the mixture to be agitated in amounts of from 0.01 to 5 parts, preferably 0.1 to 1 part, per 1000 parts by weight of Water present.

The silicone resin employed is a soluble resin having the recurring structure Si-O wherein R and R" are each independently a hydrocarbyl radical of 1-20 carbon atoms, e.g., alkyl, aryl, alkaryl and aralkyl and one of R or R" may be hydrogen, and n is an integer of between about and about 2000, and wherein the resin may be modified with up to 4 percent (0-4) hydroxy function. The silicone resin is present in the mixture to be agitated in an amount of between about 0.01 to 30 parts per 1000 parts of filled tetrafluoroethylene polymer blend. By soluble is meant that the resin is not crosslinked (gelled) and therefore is soluble in the usual solvents therefor, e.g., tetrachloroethylene. Examples of silicone resins include phenyl methyl siloxane, dimethyl siloxane containing 0.5 percent hydroxy function, monophenyl siloxane containing 1.5 percent hydroxy function, monophenyl siloxane containing 4.0 percent hydroxy function, and propyl phenyl siloxane.

The amino-functional organosilane and the silicone resin are employed simultaneously. The combination is particularly effective for filler concentrations of about 20 percent or more by volume, as either one used alone at the higher filler content does not prevent loss as effectively as the synergistic action of both together. Moreover, the mixture is effective for some fillers which do not respond to each alone.

The order in which the ingredients of the mixture to be agglomerated are mixed together is not important. Usually, the water is heated to the desired temperature and the organic liquid containing the desired amount of silicone resin is added, followed by adding the silane, then the blend.

The mixture will ordinarily contain from about 5 to about 30 percent by volume solids.

The mixture is slurried by agitation whereupon agglomeration of the initial blend occurs. The degree of agitation is not critical and can be varied to obtain particles of the size desired. The degree, temperature and time of agitation are interdependent, e.g., with more vigorous agitation, shorter times can be used. Generally, the mixture can be agitated for between about 5 and minutes at a temperature of between about 0 and about 100C. provided the temperature is not high enough to cause boiling at the pressure used. For con venience, the agitation may ordinarily be carried out between 1090C., and preferably between 2570C. Pressure is not critical and the agitation is usually carried out at atmospheric pressure in a ordinary baffled treatment vessel. The agitation may be varied during the preparation, usually by reducing the agitation during the process, e.g., from agitation at a power of 7-16 kg.m./sec./l. to a power of 02-15 kg.m./sec./l., but such is not necessary.

Following agitation, the resulting agglomerated blend is separated from the liquid medium by filtration which removes mainly the water phase, followed by drying, preferably in equipment which permits recovery of the organic liquid. Al'though drying can be carried out at temperatures up to just below the sinter temperature of the tetrafluoroethylene polymer, drying is usually carried out at between 125C. and 200C.

The resulting dried agglomerates are useful for ram extrusion and for molding, e.g., in automatic molding equipment to mold articles which can be sintered to high quality shaped articles.

The invention is more specifically illustrated in the following examples.

In the examples the standard specific gravity (SSG) of the polytetrafluoroethylene is determined by water displacement of a standard molded test specimen based upon ASTM D-1457-69. The procedure employed comprises molding the test specimen by preforming a l2-gram sample of polytetrafluoroethylene powder at 8000 psi (352 kg/cm in a mold 1 /8 inches in diameter (2.86 cm). The preform is placed in an oven preheated to 300C. The temperature of the oven is then raised to 380C. at the rate of 2C. per minute. The temperature of the oven is maintained at 380C. for 30 minutes and the oven is then cooled to 295C. at a rate of 1C. per minute. The temperature is maintained at 295C. for 25 minutes after which the test specimen is removed, allowed to cool to room temperature and the specimen tested for specific gravity (ASTM 792-66).

The term apparent density (AD), as used herein, is measured by pouring 50 g of sample into a 100 cc graduated cylinder and the volume measured without tapping.

Tensile strength (TS) and elongation are determined in accordance with ASTM D-1457-69, but using the modified thermal cycle as described above under standard specific gravity.

Average particle size is determined by a dry sieving procedure, as follows:

The sieve set (7.62 cm.) is assembled in order, with the largest opening on top. The openings are:

18 mesh 1000 micron 25 707 35 500 45 350 60 250 80 177 120 125 grams of the powder to be tested, weighed to the nearest i 0.01 gram, is charged to the top screen. The screen set is hand shaken for about 3 minutes.

After shaking, the weight of material retained on 6 Gross Tare Net C umula- Sieve No. Wt. Wt. Wt. X10 tive 7c -Continued Gross Tare Net Cumula- Sieve No. Wt. Wt. Wt. X10 tive 7c 25 707 95.57 93.27 23 33.0 35 500 94.31 91.01 33 66.0 45 350 91.58 89.22 23.6 89.6 250 88.04 87.20 8.4 98.0 177 90.69 90.59 1.0 99.0 84.60 84.60 0 99.0 170 88 230 63 325 44 Fan The average particle size and size distribution are determined by plotting the cumulative percentage vs. size on log-probability paper. The average particle size is read from the plot at the 50 percentage abscissa.

The percent mold shrinkage (MS) is determined by measuring the diameter of the molded chip used to determine SSG after sintering, using the equation:

mold diameter-chip diameter MS X 100 mold diameter The filler content was determined by decomposing the polymer in a muffle furnace under nitrogen and weighing the remaining filler.

EXAMPLE 1 This example in runs 1 and 2 illustrates the process of this invention. Comparing results with the comparison run shows the better filler retention in the process of this invention.

Agitation was carried out in a stainless steel vessel 15.24 cm. in diameter and 20.32 cm. deep, equipped with two baffles 1.27 cm. wide. The stirrer used was 7.62 cm. in diameter, having 4 blades, each 1.27 cm. wide with a 45 downdraft pitch. Sixteen hundred ml of dimineralized water was charged to the vessel and heated to the temperature shown in the following Tables.

The organic liquid employed was tetrachloroethylene in an amount of 81 gm (50 ml).

The amino-functional organosilane 'y-aminopropyl triethoxysilane.

The silicone resin used was phenyl methyl siloxane (Dow Corning 805).

The tetrafluoroethylene polymer used was polytetrafluoroethylene wherein the resin particles had an average size of about 35 u. 200 Gm of PTFE/filler blend was used in each run. I

The filler used was glass fiber having a maximum length of about 0.078 cm. length and 1 1 micron diameter in an amount of 40 percent by weight of the blend (less than 40 percent by volume).

Additional data is shown in Table l-A following. Agitation was started at 1000 rpm at 40C. and continued for 5 minutes, then reduced to 600 rpm for 25 minutes at 40C. After agitation, the agglomerated product was recovered by draining the mixture onto a screen with 250 micron size openings. The dewatered product was then dried in a vacuum oven at C. Characteristics of the agglomerated product of each run are also shown in Table l-B.

used was TABLE l-A cc Amino gm Silicone 7: Glass Run lane Resin In Product Comparison 0.5 O 32.6 1 0.5 0.05 38.8 2 0.5 0.2 39.7

As can be seen in Table l-A, more filler is retained in the product using both the silane and the silicone.

TABLE l-B Properties of the products of Table l-A are as follows, and show usefulness of the products as molding powders.

This example was carried out using the equipment, ingredients and procedures set forth in Example 1, except that the starting blend contained 25 percent by weight of glass. Results are shown in Tables 2-A and 2-B.

TABLE 2-A cc Amino gm Silicone 7: Glass Run Silane Resin In Product Comparison 0.5 20.5 1 0.5 0.005 22.4 2 0.5 0.05 25.2 (within experimental error of starting material) As can be seen in Table 2-A, more filler is retained where both the silane and the silicone are employed.

TABLE 2-B Properties of the products of Table 2-A are as follows, and show usefulness of the products as molding powders.

Average TS/ Particle AD Elonga- Size Run g/l 850 MS tion (u) Comparison 877 2.21 1 1.68 2860/263 680 1 909 2.207 1.50 2410/232 730 2 877 2.193 1.33 2010/17) 670 The same procedure was carried out using 0.5 cc of the aminosilane and 2.0 gm of silicone with satisfactory results.

EXAMPLE 3 This example was carried out as was Example 2 except that the tiller employed was alumina (Alundum) particles of a size of less than 60 microns in an amount of 25 percent by weight of the blend. Results are set forth in Table 3.

As can be seen more filler is retained when both the silane and the silicone resin are employed.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. In the process for preparing filled agglomerated granules of non-melt-fabricable granular tetrafluoroethylene polymer in which the filler is a particulate hydrophilic filler present in an amount of between about 5 percent and 40 percent by volume of the total volume, by agitating a finely divided blend of said polymet and said filler in which the particle size of the finely divided tetrafluoroethylene polymer averages numerically below about 200 microns and in which the tiller is present in an amount of between about 5 percent and 40 percent by volume, in a two-phase liquidmedium consisting essentially of water and an organic liquid which is soluble in water up to at most 15 percent by weight at the operating temperature of the process and which has a surface tension no greater than about 40 dynes/cm. at 25C., and in which the organic liquid is present in an amount of 0.1 to 0.5 cc per gram of said blend, the improvement wherein said liquid medium contains an amino-functional organosilane present in an amount of between 0.01 and 5 parts per 1000 parts by weight of water and a silicone resin soluble in said organic liquid and present in an amount of between 0.01 and 30 parts per 1000 parts by weight of said finely divided blend, said liquid mixture containing said blend having between about 5-30 percent by weight solids content.

2. The process of claim 1 wherein the filler is glass. 3. The process of claim 1 wherein the organosilane is represented by the formula wherein A is a water-hydrolyzable functional group, B is an aliphatic or aromatic hydrocarbyl group of 1-14 carbon atoms containing amino-functionality, and each D is A, B, alkyl of l-5 carbon atoms, aryl of 6-10 carbon atoms, alkaryl of 7-10 carbon atoms, or aralkyl of 7-10 carbon atoms.

4. The process of claim 3 wherein the filler is glass.

5. The process of claim 3 wherein the agitation is carried out at a temperature of between 0 and almost C, provided the temperature is not high enough to cause boiling of the liquid medium.

6. The process of claim 4 wherein the silicone resin is represented by the formula Ei-O wherein each R and R" is a hydrocarbyl group of 1-20 carbon atoms and. one of R and R" may be hydrogen;

n is an integer of between about 100 and 2000, and said 9. The process of claim 8 wherein the filler is glass. 

1. IN THE PROCESS FOR PREPARING FILLED AGGLOMERATED GRANULES OF NON-MELT-FABRICABLE GRANULAR TETRAFLUOROETHYLENE POLYMER IN WHICH THE FILLER IS A PARTICULATE HYDROPHILIC FILLER PRESENT AN AMOUNT OF BETWEEN ABOUT 5 PERCENT AND 40 PERCENT BY VOLUME OF THE TOTAL VOLUME, BY AGITATING A FINELY DIVIDED BLEND OF SAID POLYMER AND SAID FILLER IN WHICH THE PARTICLE SIZE OF THE FINELY DIVIDED TETRAFLUOROETHYLENE POLYMER AVERAGES NUMERICALLY BELOW ABOUT 200 MICRONS AND IN WHICH THE FILLER IS PRESENT IN AN AMOUNT OF BETWEEN ABOUT 5 PERCENT AND 40 PERCENT BY VOLUME, IN A TWO-PHASE LIQUID MEDIUM CONSISTING ESSENTIALLY OF WATER AND AN ORGANIC LIQUID WHICH IS SOLUBLE IN WATER UP TO AT MOST 15 PERCENT BY WEIGHT AT THE OPERATING TEMPERATURE OF THE PROCESS AND WHICH HAS A SURFACE TENSION NO GREATER THAN ABOUT 40 DYNES/CM. AT 25*C., AND IN WHICH THE ORGANIC LIQUID IS AN AMOUNT OF 0.1 TO 0.5 CC PER GRAM OF SAID BLEND, THE IMPROVEMENT WHEREIN SAID LIQUID MEDIUM CONTAINS AN AMINO-FUNCTIONAL ORGANOSILANE PRESENT IN AN AMOUNT OF BETWEEN 0.01 AND 5 PARTS PER 1000 PARTS BY WEIGHT OF WATER AND A CILICONE RESIN SOLUBLE IN SAID ORGANIC LIQUID AND PRESENT IN AMOUNT OF BETWEEN 0.10 AND 30 PARTS PER 1000 PARTS BY WEIGHT OF SAID FINELY DIVIDED BLEND, SAID LIQUID MIXTURE CONTAINING SAID BLEND HAVING BETWEEN ABOUT 5-30 PERCENT BY WEIGHT SOLIDS CONTENT.
 2. The process of claim 1 wherein the filler is glass.
 3. The process of claim 1 wherein the organosilane is represented by the formula
 4. The process of claim 3 wherein the filler is glass.
 5. The process of claim 3 wherein the agitation is carried out at a temperature of between 0 and almost 100* C., provided the temperature is not high enough to cause boiling of the liquid medium.
 6. The process of claim 4 wherein the silicone resin is represented by the formula 8n
 7. The process of claim 6 wherein the organic liquid is tetrachloroethylene.
 8. The process of claim 5 wherein the organic liquid is tetrachloroethylene.
 9. The process of claim 8 wherein the filler is glass. 